CN1257564C - Composite polymer diaphram used for secondary lithium battery and its preparation technology - Google Patents
Composite polymer diaphram used for secondary lithium battery and its preparation technology Download PDFInfo
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- CN1257564C CN1257564C CNB031008135A CN03100813A CN1257564C CN 1257564 C CN1257564 C CN 1257564C CN B031008135 A CNB031008135 A CN B031008135A CN 03100813 A CN03100813 A CN 03100813A CN 1257564 C CN1257564 C CN 1257564C
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Abstract
The present invention belongs to the technical field of preparing a critical material of a secondary lithium battery. On the basis of a phase inversion method, the present invention adds inorganic powder materials, uses the method such as the mixing method of evaporation control and immersion deposition, an immersion deposition method, etc. to prepare a composite polymer membrane. The membrane has the characteristics of high porosity factor, good mechanical strength, simple process, easy operation and low cost, and the membrane can satisfy practical application requirements for the secondary lithium battery. The present invention can be also used for ultrafiltration membranes, microfiltration membranes, etc. for separation between liquids.
Description
Technical field: the invention belongs to preparation lithium secondary battery critical material and technical field.
Background technology: Telcodia Technologies (predecessor of Bellcore company) has reported in 1994 with the PVdF-HFP copolymer and has been used for preparation and assembling plastic lithium ion battery.This method is PVdF, additive SiO
2Stir 30 minutes mixings with DBP under 140 ℃ of conditions, the mixture that obtains forms film 150 ℃ of following hot pressing again, soaks in ether at last and removes DBP in 2 minutes.The apparent one-tenth opaque white color of Bellcore barrier film has higher porosity, inhales the PC amount under the room temperature and can reach 118% of deadweight.Because this film-forming process has solvent extraction, increases process complexity to a certain extent, and large-scale production is also had certain restriction.
Prepare membrane for polymer with phase inversion and can overcome the inconvenient factor that solvent extraction is brought, it is a kind ofly to make polymer change solid-state process into from liquid state with certain control mode, and this solidification process changes owing to a homogeneous phase is liquid normally that two liquid state (layering of liquid liquid) cause.When layering acquired a certain degree, one of them liquid phase (phase that polymer concentration is high) was solidified, and the result has formed solid body.Can prepare the porous polymer membrane that is used for lithium secondary battery by methods such as the control in the phase inversion evaporation precipitation method, immersion precipitation or both mix.
But because the said method barrier film mechanical performance of making is relatively poor, porosity is relatively low, be used for assembled battery after effect not very good.
The object of the present invention is to provide and have the composition polymer barrier film that better charge-discharge performance is arranged after certain mechanical strength, the assembled battery.In system, add inorganic powder, can improve conductivity, increase barrier film heat and mechanically stable scope, better electrochemical stability window is arranged, improve the compatibility of lithium electrode and electrolyte interface.Lithium secondary battery with composition polymer barrier film preparation of the present invention can have better chemical property.
Summary of the invention:
The composition polymer barrier film that the present invention is prepared with microcellular structure, it is characterized in that: added pore-foaming agent or/and inorganic powder, wherein pore-foaming agent is selected from low-molecular-weight polyethylene glycol, butanone, 1,4-butanediol, phosphoric acid, triethyl phosphate, ethylene glycol monoemethyl ether, poly-ethyl pyrrolidone, diethylamine, NaNO
3, LiCl, NH
4Cl; Inorganic powder is selected from AlN, Al
2O
3, BaTiO
3, LiNbO
3, LiAlO
2, Bi
2O
3, B
4C, BN, CaSiO
3, CeO
2, Fe
2O
3, MoS
2, PbTiO
3, SiC, Si
3N
4, SiO
2, TiB
2, TiO
2, WC, ZrO
2, MgO, AlBr
3, zeolite molecular sieve, glass fibre, the particle size of inorganic powder is 10nm-1 μ m; The basic structure of composition polymer barrier film is that pore-foaming agent or inorganic powder are distributed in polymer surfaces and inside or the barrier film hole, form the symmetry or the dissymmetrical structure of finger-like or spongy three-dimensional network, and aperture size, pattern with the difference of the kind of inorganic powder, particle diameter difference.
The object of the present invention is achieved like this: each component material for preparing composition polymer barrier film of the present invention comprises:
(1) thermoplastic polymer: water insoluble and organic solvent (comprises ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, gamma-butyrolacton, dimethyl-tetrahydrofuran) and have the polymeric film material of good chemical and electrochemical stability, as Kynoar (PVdF) and copolymer thereof, polyacrylonitrile (PAN) and copolymer thereof, polyvinyl alcohol (PVA) and copolymer thereof, polyethylene (PE), polypropylene (PP), polyacrylate and derivative thereof, polysulfones (PSf), polyether sulfone (PES), polybutylene terephthalate (PBT) and copolymer thereof, PETG (PET) and copolymer thereof, Merlon (PC) and copolymer thereof, polyamide (PA) and copolymer thereof, polyimides (PI) and copolymer thereof, polyurethane (PU) and copolymer thereof.
(2) solvent: the energy dissolve polymer, as acetone, N, dinethylformamide, N, the N-diethyl acetamide, triethyl phosphate, oxolane, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), benzene, toluene, dimethylbenzene, chlorobenzene, isobutanol, β-ethoxy ethanol, 1,4-dioxane, diisopropyl ketone, acetate, isobutyric acid, methyl formate, ethyl acetate, acetate, cyclohexanol, isobutyl propionate, butyl lactate, carrene, chloroform, carbon tetrachloride, cyclohexane, pentane, sulfolane, cyclohexanone, methylethylketone, N-methyl caprolactam, the hexane phosphamide, tetramethylurea, triethyl phosphate, trimethyl phosphate, hydroxyacetonitrile, chloroacetonitrile, adiponitrile, first and second sulfones.
(3) non-solvent: can not dissolve polymer, but can and solvent dissolve each other, as methyl alcohol, ethanol, propyl alcohol, n-butanol, isobutanol, ethylene glycol, glycerol, cyclobutanol, cyclohexanol, water, ether, isopropyl ether, metacresol, naphthane, decahydronaphthalene.
(4) coagulating bath: how in immersion precipitation, to use.Can be water, methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, the mixing of solvent and water is bathed.
(5) inorganic powder: inorganic matter with high-specific surface area.As AlN, Al
2O
3, BaTiO
3, LiNbO
3, LiAlO
2, Bi
2O
3, B
4C, BN, CaSiO
3, CeO
2, Fe
2O
3, MoS
2, PbTiO
3, SiC, Si
3N
4, SiO
2, TiB
2, TiO
2, WC, ZrO
2, MgO, AlBr
3, zeolite molecular sieve, glass fibre.
(6) pore-foaming agent: can be low-molecular-weight polyethylene glycol (PEG), butanone, 1,4-butanediol, phosphoric acid, triethyl phosphate, ethylene glycol monoemethyl ether, poly-ethyl pyrrolidone, diethylamine, NaNO
3,, LiCl, NH
4Cl.
Composition polymer barrier film of the present invention prepares according to the following steps:
(1) adopts control evaporation-immersion precipitation mixing method: polymer and inorganic powder, solvent and non-solvent are mixed, heating stirs into an even gel liquid, inorganic powder accounts for 0.2-6%, polymer accounts for 10-12%, solvent accounts for 75-84%, non-solvent accounts for 5-10%, and the method is used lower, the volatile solvent of boiling point; After static 2-20min sloughs bubble, under the room temperature condition coagulant liquid is coated on clean glass plate, polyester or the metal matrix by roll-in, blade coating, curtain coating or casting method; Coagulant liquid at humidity 30-80%, is solidified 0-20min under temperature 20-45 ℃ the condition, form nascent film; Then nascent symphysis is contained in the coagulating bath of 0-50% solvent with the matrix immersion, form wet film, coagulation bath temperature is lower than solvent boiling point, immerses time 10min-12hr; Take out wet film after air drying is removed most of water, put into vacuum drying oven 30-100 ℃ again and promptly obtain aperture size 5-20 μ m behind the dry 0.5-24hr down, porosity 40-80%, thickness are the composition polymer barrier film of 20-300 μ m; Or
(2) adopt immersion precipitation: polymer, inorganic powder, pore-foaming agent and solvent heating are stirred to are the transparent and homogeneous coagulant liquid, polymer accounts for 10-25%, inorganic powder accounts for the 2-40% of polymer weight, pore-foaming agent accounts for the 0-30% of polymer weight, and the method is used higher solvent or higher boiling point and the lower boiling mixed solvent of boiling point; The coagulant liquid coating process obtains nascent film with control evaporation-immersion precipitation mixing method; It is placed on air drying with matrix, humidity 30-80%, temperature 20-45 ℃, drying time, 0-20min contained nascent symphysis in the coagulating bath of 0-50% solvent with the matrix immersion then, and coagulation bath temperature is lower than solvent boiling point, immerses time 10min-12hr; Again film is put into 30-100 ℃ the dry 0.5-24hr of vacuum drying chamber subsequently, or in 55-65 ℃ the hot bath, removed residual solvent, rock-steady structure, the composition polymer membrane pore size size 20nm-20 μ m that the method makes, porosity is 3-70%; Or
(3) adopt the vapor phase precipitation method: polymer, inorganic powder, solvent heating are stirred to and are the transparent and homogeneous coagulant liquid, and polymer accounts for 10-30%, and inorganic powder accounts for the 2-40% of polymer weight; Being coated in the pre-saturated obturator of solvent vapour of coagulant liquid carried out, and temperature remains on 20 ℃ in the device, and feeds the nitrogen current that is mixed with the non-solvent steam; Regulate non-solvent steam and nitrogen relative scale, make the former scope be controlled at 65-100%; Coagulant liquid is coated on clean glass plate, polyester or the metal matrix by roll-in or blade coating; The symphysis that coats is placed 3-8hr with matrix in this device, and then immerse 20 ℃ non-solvent bathe in the 30min-4hr rock-steady structure, the method makes aperture size 5-20 μ m, porosity 20-70%, symmetrical decorticate composition polymer barrier film.
The invention has the advantages that: the barrier film of preparation has certain mechanical strength, and better charge-discharge performance is arranged after the assembled battery.In system, add inorganic powder, can control membrane pore size size and pattern according to its kind, particle size, and can improve conductivity, increase barrier film heat and mechanically stable scope, have better electrochemical stability window, improve the compatibility of lithium electrode and electrolyte interface.
Description of drawings
Below in conjunction with chart and embodiment the present invention is done further narration:
Fig. 1 is the stereoscan photograph of the embodiment of the invention 1 barrier film,
Fig. 2 is the stereoscan photograph of the embodiment of the invention 7 barrier films,
Fig. 3 is the stereoscan photograph of the embodiment of the invention 12 barrier films,
Fig. 4 is the stereoscan photograph of the embodiment of the invention 13 barrier films,
Fig. 5 is the charging and discharging curve of embodiment 6 principle batteries,
Fig. 6 is the charging and discharging curve of embodiment 7 principle batteries.
Table 1 is for discharging and recharging tables of data.
Specific implementation method:
[embodiment 1]
Acetone solvent is added in the Kynoar (model is Kynar 2801), and heating stirs to clarify, and adds deionized water then.Their weight ratio is 16/2/1.Get the transparent and homogeneous coagulant liquid after continuing to add thermal agitation 30min.Coagulant liquid is left standstill 5min remove air bubble.Before coating, scraper and glass plate matrix are wiped clean with acetone and ethanol.The film that coats be placed in the air of 20 ℃ of temperature, humidity 50% that solvent partly volatilizees, after the gel primary solidification, together be immersed in 30min in 20 ℃ the water-bath together with matrix, take out the back and remove most of water at air drying, put it into again in 40 ℃ the vacuum drying chamber and dry by the fire 4hr, 80 ℃ down baking 12hr remove non-solvent and solvent.The stereoscan photograph of barrier film is seen Fig. 1.
It is 70% that porosity is surveyed with n-butanol in barrier film oven dry back, and pore size is 8 μ m.It is cut into 1.77cm
2Disk is made the work electrode with native graphite, and lithium metal is done electrode, and electrolyte adopts 1M LiPF
6-EC/DEC (vol 1: 1) is assembled into the principle battery in the argon gas glove box, survey its chemical property.
Adopt the battery performance test instrument Experimental cell to be carried out the test of charge and discharge cycles.The charging cut-ff voltage is to 2.0V, and discharge cut-off voltage is to 0.005V.Discharge and recharge data and see Table 1.
[embodiment 2]
With average grain diameter is SiO about 10nm
2Join in Kynoar (model the is Kynar 2801) powder nanometer SiO
2Content account for 10% of polymer body.Add acetone again, heating stirs to clarify, and adds deionized water then.Polymer, the weight ratio of acetone and deionized water are 2/16/1.Get the transparent and homogeneous coagulant liquid after continuing to stir 45min.Coagulant liquid is left standstill 5min remove air bubble.Before coating, scraper and glass plate matrix are wiped clean with acetone and ethanol.The film that coats be placed in the air of 20 ℃ of temperature, humidity 50% that solvent partly volatilizees, after the gel primary solidification, together be immersed in 30min in 20 ℃ the water-bath together with matrix, take out the back and remove most of water at air drying, put it into again in 40 ℃ the vacuum drying chamber and dry by the fire 4hr, 80 ℃ down baking 12hr remove non-solvent and solvent.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 3]
To be the SiO about 10nm through special surface processing (inorganic agent comprises silanes and titanate ester), average grain diameter
2Join in Kynoar (model the is Kynar 2801) powder nanometer SiO
2Content account for 10% of polymer body.Add acetone again, heating stirs to clarify, and adds deionized water then.Polymer, the weight ratio of acetone and deionized water are 2/16/1.Get the transparent and homogeneous coagulant liquid after continuing to stir 45min.Coagulant liquid is left standstill 5min remove air bubble.Before coating, scraper and glass plate matrix are wiped clean with acetone and ethanol.The film that coats be placed in the air of 20 ℃ of temperature, humidity 50% that solvent partly volatilizees, after the gel primary solidification, together be immersed in 30min in 20 ℃ the water-bath together with matrix, take out the back and remove most of water at air drying, put it into again in 40 ℃ the vacuum drying chamber and dry by the fire 4hr, 80 ℃ down baking 12hr remove non-solvent and solvent.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 4]
With particle mean size is α-Al about 150nm
2O
3Join in Kynoar (model the is Kynar 2801) powder nanometer α-Al
2O
3Content account for 10% of polymer body.Add acetone again, heating stirs to clarify, and adds deionized water then.Polymer, the weight ratio of acetone and deionized water are 2/16/1.Get the transparent and homogeneous coagulant liquid after continuing to stir 45min.Coagulant liquid is left standstill 5min remove air bubble.Before coating, scraper and glass plate matrix are wiped clean with acetone and ethanol.The film that coats be placed in the air of 20 ℃ of temperature, humidity 50% that solvent partly volatilizees, after the gel primary solidification, together be immersed in 30min in 20 ℃ the water-bath together with matrix, take out the back and remove most of water at air drying, put it into again in 40 ℃ the vacuum drying chamber and dry by the fire 4hr, 80 ℃ down baking 12hr remove non-solvent and solvent.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 5]
To be the α-A1 about 150nm through special surface processing (inorganic agent comprises silanes and titanate ester), particle mean size
2O
3Join in Kynoar (model the is Kynar 2801) powder nanometer α of modified mistake-Al
2O
3Content accounts for 10% of polymer body.Add acetone again, heating stirs to clarify, and adds deionized water then.Polymer, the weight ratio of acetone and deionized water are 2/16/1.Get the transparent and homogeneous coagulant liquid after continuing to stir 45min.Coagulant liquid is left standstill 5min remove air bubble.Before coating, scraper and glass plate matrix are wiped clean with acetone and ethanol.The film that coats be placed in the air of 20 ℃ of temperature, humidity 50% that solvent partly volatilizees, after the gel primary solidification, together be immersed in 30min in 20 ℃ the water-bath together with matrix, take out the back and remove most of water at air drying, put it into again in 40 ℃ the vacuum drying chamber and dry by the fire 4hr, 80 ℃ down baking 12hr remove non-solvent and solvent.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 6]
With particle mean size is γ-Al about 60nm
2O
3Join in Kynoar (model the is Kynar 2801) powder nanometer γ-Al
2O
3Content account for 10% of polymer body.Add acetone again, heating stirs to clarify, and adds deionized water then.Polymer, the weight ratio of acetone and deionized water are 2/16/1.Get the transparent and homogeneous coagulant liquid after continuing to stir 45min.Coagulant liquid is left standstill 5min remove air bubble.Before coating, scraper and glass plate matrix are wiped clean with acetone and ethanol.The film that coats be placed in the air of 20 ℃ of temperature, humidity 50% that solvent partly volatilizees, after the gel primary solidification, together be immersed in 30min in 20 ℃ the water-bath together with matrix, take out the back and remove most of water at air drying, put it into again in 40 ℃ the vacuum drying chamber and dry by the fire 4hr, 80 ℃ down baking 12hr remove non-solvent and solvent.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1, charging and discharging curve is seen Fig. 5.
[embodiment 7]
With particle mean size is rutile phase TiO about 40nm * 10nm
2Join in Kynoar (model the is Kynar 2801) powder nano-TiO
2Content accounts for 10% of polymer body.Add acetone again, heating stirs to clarify, and adds deionized water then.Polymer, the weight ratio of acetone and deionized water are 2/16/1.Get the transparent and homogeneous coagulant liquid after continuing to stir 45min.Coagulant liquid is left standstill 5min remove air bubble.Before coating, scraper and glass plate matrix are wiped clean with acetone and ethanol.The film that coats be placed in the air of 20 ℃ of temperature, humidity 50% that solvent partly volatilizees, after the gel primary solidification, together be immersed in 30min in 20 ℃ the water-bath together with matrix, take out the back and remove most of water at air drying, put it into again in 40 ℃ the vacuum drying chamber and dry by the fire 4hr, 80 ℃ down baking 12hr remove non-solvent and solvent.The stereoscan photograph of barrier film is seen Fig. 2.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1, charging and discharging curve is seen Fig. 6.
[embodiment 8]
To handle (inorganic agent comprises silanes and titanate ester), particle mean size through special surface is rutile TiO mutually about 40nm * 10nm
2Join in Kynoar (model the is Kynar 2801) powder nano-TiO of modified mistake
2Content account for 10% of polymer body.Add acetone again, heating stirs to clarify, and adds deionized water then.Polymer, the weight ratio of acetone and deionized water are 2/16/1.Get the transparent and homogeneous coagulant liquid after continuing to stir 45min.Coagulant liquid is left standstill 5min remove air bubble.Before coating, scraper and glass plate matrix are wiped clean with acetone and ethanol.The film that coats be placed in the air of 20 ℃ of temperature, humidity 50% that solvent partly volatilizees, after the gel primary solidification, together be immersed in 30min in 20 ℃ the water-bath together with matrix, take out the back and remove most of water at air drying, put it into again in 40 ℃ the vacuum drying chamber and dry by the fire 4hr, 80 ℃ down baking 12hr remove non-solvent and solvent.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 9]
With particle mean size is that 13X type molecular sieve about 1 μ m joins in Kynoar (model the is Kynar 2801) powder, and the 13X molecular sieve content accounts for 10% of polymer body.Add acetone again, heating stirs to clarify, and adds deionized water then.Polymer, the weight ratio of acetone and deionized water are 2/16/1.Get the transparent and homogeneous coagulant liquid after continuing to stir 45min.Coagulant liquid is left standstill 5min remove air bubble.Before coating, scraper and glass plate matrix are wiped clean with acetone and ethanol.The film that coats be placed in the air of 20 ℃ of temperature, humidity 50% that solvent partly volatilizees, after the gel primary solidification, together be immersed in 30min in 20 ℃ the water-bath together with matrix, take out the back and remove most of water at air drying, put it into again in 40 ℃ the vacuum drying chamber and dry by the fire 4hr, 80 ℃ down baking 12hr remove non-solvent and solvent.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 10]
With particle mean size is that 13X type molecular sieve about 1 μ m carries out ion-exchange with LiCl solution, be replaced as Li type molecular sieve after, join in Kynoar (model the is Kynar 2801) powder, Li type molecular sieve content accounts for 10% of polymer body.Add acetone again, heating stirs to clarify, and adds deionized water then.Polymer, the weight ratio of acetone and deionized water are 2/16/1.Get the transparent and homogeneous coagulant liquid after continuing to stir 45min.Coagulant liquid is left standstill 5min remove air bubble.Before coating, scraper and glass plate matrix are wiped clean with acetone and ethanol.The film that coats be placed in the air of 20 ℃ of temperature, humidity 50% that solvent partly volatilizees, after the gel primary solidification, together be immersed in 30min in 20 ℃ the water-bath together with matrix, take out the back and remove most of water at air drying, put it into again in 40 ℃ the vacuum drying chamber and dry by the fire 4hr, 80 ℃ down baking 12hr remove non-solvent and solvent.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 11]
With particle mean size is that 4A type molecular sieve about 1 μ m joins in Kynoar (model the is Kynar 2801) powder, and the 4A molecular sieve content accounts for 10% of polymer body.Add acetone again, heating stirs to clarify, and adds deionized water then.Polymer, the weight ratio of acetone and deionized water are 2/16/1.Get the transparent and homogeneous coagulant liquid after continuing to stir 45min.Coagulant liquid is left standstill 5min remove air bubble.Before coating, scraper and glass plate matrix are wiped clean with acetone and ethanol.The film that coats be placed in the air of 20 ℃ of temperature, humidity 50% that solvent partly volatilizees, after the gel primary solidification, together be immersed in 30min in 20 ℃ the water-bath together with matrix, take out the back and remove most of water at air drying, put it into again in 40 ℃ the vacuum drying chamber and dry by the fire 4hr, 80 ℃ down baking 12hr remove non-solvent and solvent.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 12]
With Kynoar (model is Kynar 2801) powder, the N-methyl pyrrolidone is with 1/4 mixed, and heating is stirred to and is a transparent even gel, leaves standstill the air bubble in removing gel then.In humidity is 30%, under the condition that temperature is 20 ℃, is coated with on clean glass plate.After placing 5min, nascent symphysis together is immersed in 4hr in 25 ℃ the water-bath with matrix, the vacuum drying chamber of putting into 40 ℃ after the taking-up dries by the fire 4hr, dries by the fire 12hr down at 100 ℃ again, removes moisture and solvent to obtain stable membrane structure.The stereoscan photograph of barrier film is seen Fig. 3.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 13]
With average grain diameter is SiO about 10nm
2Join in Kynoar (model the is Kynar 2801) powder nanometer SiO
2Content account for 10% of polymer body.Add the N-methyl pyrrolidone again as solvent, it and Kynoar weight ratio are 4/1.Heating is stirred to and is a transparent even gel, leaves standstill the air bubble in removing gel then.In humidity is 30%, under the condition that temperature is 20 ℃, is coated with on clean glass plate.After placing 5min, nascent symphysis together is immersed in 4hr in 25 ℃ the water-bath with matrix, the vacuum drying chamber of putting into 40 ℃ after the taking-up dries by the fire 4hr, dries by the fire 12hr down at 100 ℃ again, removes moisture and solvent to obtain stable membrane structure.The stereoscan photograph of barrier film is seen Fig. 4.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 14]
To be the SiO about 10nm through special surface processing (inorganic agent comprises silanes and titanate ester), average grain diameter
2Join in Kynoar (model the is Kynar 2801) powder nanometer SiO
2Content account for 10% of polymer body.Add the N-methyl pyrrolidone again as solvent, it and Kynoar weight ratio are 4/1.Heating is stirred to and is a transparent even gel, leaves standstill the air bubble in removing gel then.In humidity is 30%, under the condition that temperature is 20 ℃, is coated with on clean glass plate.After placing 5min, nascent symphysis together is immersed in 4hr in 25 ℃ the water-bath with matrix, the vacuum drying chamber of putting into 40 ℃ after the taking-up dries by the fire 4hr, dries by the fire 12hr down at 100 ℃ again, removes moisture and solvent to obtain stable membrane structure.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 15]
With particle mean size is α-Al about 150nm
2O
3Join in Kynoar (model the is Kynar 2801) powder nanometer α-Al
2O
3Content account for 10% of polymer body.Add the N-methyl pyrrolidone again as solvent, it and Kynoar weight ratio are 4/1.Heating is stirred to and is a transparent even gel, leaves standstill the air bubble in removing gel then.In humidity is 30%, under the condition that temperature is 20 ℃, is coated with on clean glass plate.After placing 5min, nascent symphysis together is immersed in 4hr in 25 ℃ the water-bath with matrix, the vacuum drying chamber of putting into 40 ℃ after the taking-up dries by the fire 4hr, dries by the fire 12hr down at 100 ℃ again, removes moisture and solvent to obtain stable membrane structure.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 16]
To be the α-Al about 150nm through special surface processing (inorganic agent comprises silanes and titanate ester), particle mean size
2O
3Join in Kynoar (model the is Kynar 2801) powder nanometer α of modified mistake-Al
2O
3Content accounts for 10% of polymer body.Add the N-methyl pyrrolidone again as solvent, it and Kynoar weight ratio are 4/1.Heating is stirred to and is a transparent even gel, leaves standstill the air bubble in removing gel then.In humidity is 30%, under the condition that temperature is 20 ℃, is coated with on clean glass plate.After placing 5min, nascent symphysis together is immersed in 4hr in 25 ℃ the water-bath with matrix, the vacuum drying chamber of putting into 40 ℃ after the taking-up dries by the fire 4hr, dries by the fire 12hr down at 100 ℃ again, removes moisture and solvent to obtain stable membrane structure.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 17]
With particle mean size is γ-Al about 60nm
2O
3Join in Kynoar (model the is Kynar 2801) powder nanometer γ-Al
2O
3Content account for 10% of polymer body.Add the N-methyl pyrrolidone again as solvent, it and Kynoar weight ratio are 4/1.Heating is stirred to and is a transparent even gel, leaves standstill the air bubble in removing gel then.In humidity is 30%, under the condition that temperature is 20 ℃, is coated with on clean glass plate.After placing 5min, nascent symphysis together is immersed in 4hr in 25 ℃ the water-bath with matrix, the vacuum drying chamber of putting into 40 ℃ after the taking-up dries by the fire 4hr, dries by the fire 12hr down at 100 ℃ again, removes moisture and solvent to obtain stable membrane structure.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 18]
With particle mean size is rutile phase TiO about 40nm * 10nm
2Join in Kynoar (model the is Kynar 2801) powder nano-TiO
2Content accounts for 10% of polymer body.Add the N-methyl pyrrolidone again as solvent, it and Kynoar weight ratio are 4/1.Heating is stirred to and is a transparent even gel, leaves standstill the air bubble in removing gel then.In humidity is 30%, under the condition that temperature is 20 ℃, is coated with on clean glass plate.After placing 5min, nascent symphysis together is immersed in 4hr in 25 ℃ the water-bath with matrix, the vacuum drying chamber of putting into 40 ℃ after the taking-up dries by the fire 4hr, dries by the fire 12hr down at 100 ℃ again, removes moisture and solvent to obtain stable membrane structure.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 19]
To be the rutile TiO about 40nm * 10nm through special surface processing (inorganic agent comprises silanes and titanate ester), particle mean size
2Join in Kynoar (model the is Kynar2801) powder nano-TiO of modified mistake
2Content account for 10% of polymer body.Add the N-methyl pyrrolidone again as solvent, it and Kynoar weight ratio are 4/1.Heating is stirred to and is a transparent even gel, leaves standstill the air bubble in removing gel then.In humidity is 30%, under the condition that temperature is 20 ℃, is coated with on clean glass plate.After placing 5min, nascent symphysis together is immersed in 4hr in 25 ℃ the water-bath with matrix, the vacuum drying chamber of putting into 40 ℃ after the taking-up dries by the fire 4hr, dries by the fire 12hr down at 100 ℃ again, removes moisture and solvent to obtain stable membrane structure.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 20]
With particle mean size is that 13X type molecular sieve about 1 μ m joins in Kynoar (model the is Kynar 2801) powder, and the 13X molecular sieve content accounts for 10% of polymer body.Add the N-methyl pyrrolidone again as solvent, it and Kynoar weight ratio are 4/1.Heating is stirred to and is a transparent even gel, leaves standstill the air bubble in removing gel then.In humidity is 30%, under the condition that temperature is 20 ℃, is coated with on clean glass plate.After placing 5min, nascent symphysis together is immersed in 4hr in 25 ℃ the water-bath with matrix, the vacuum drying chamber of putting into 40 ℃ after the taking-up dries by the fire 4hr, dries by the fire 12hr down at 100 ℃ again, removes moisture and solvent to obtain stable membrane structure.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 21]
With particle mean size is that 13X type molecular sieve about 1 μ m carries out ion-exchange with LiCl solution, be replaced as Li type molecular sieve after, join in Kynoar (model the is Kynar 2801) powder, Li type molecular sieve content accounts for 10% of polymer body.Add the N-methyl pyrrolidone again as solvent, it and Kynoar weight ratio are 4/1.Heating is stirred to and is a transparent even gel, leaves standstill the air bubble in removing gel then.In humidity is 30%, under the condition that temperature is 20 ℃, is coated with on clean glass plate.After placing 5min, nascent symphysis together is immersed in 4hr in 25 ℃ the water-bath with matrix, the vacuum drying chamber of putting into 40 ℃ after the taking-up dries by the fire 4hr, dries by the fire 12hr down at 100 ℃ again, removes moisture and solvent to obtain stable membrane structure.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
[embodiment 22]
With particle mean size is that 4A type molecular sieve about 1 μ m joins in Kynoar (model the is Kynar 2801) powder, and the 4A molecular sieve content accounts for 10% of polymer body.Add the N-methyl pyrrolidone again as solvent, it and Kynoar weight ratio are 4/1.Heating is stirred to and is a transparent even gel, leaves standstill the air bubble in removing gel then.In humidity is 30%, under the condition that temperature is 20 ℃, is coated with on clean glass plate.After placing 5min, nascent symphysis together is immersed in 4hr in 25 ℃ the water-bath with matrix, the vacuum drying chamber of putting into 40 ℃ after the taking-up dries by the fire 4hr, dries by the fire 12hr down at 100 ℃ again, removes moisture and solvent to obtain stable membrane structure.
The Integration Assembly And Checkout of principle battery is with embodiment 1.Discharge and recharge data and see Table 1.
Table 1
| The embodiment numbering | Reversible capacity | First all efficient | Second all efficient |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 | 302 310 312 306 308 304 315 300 283 292 285 302 306 305 310 311 288 301 292 311 310 308 | 86.3 88.5 88.9 87.2 88.4 87.3 89.2 86.2 82.9 84.6 85.0 86.6 87.6 87.5 88.7 88.8 83.5 86.3 84.5 88.9 88.7 88.0 | 98.2 98.3 98.8 98.2 96.6 97.1 98.0 96.6 98.1 98.7 94.5 98.3 98.4 98.2 98.8 98.1 95.4 97.6 96.8 98.2 98.5 96.6 |
Claims (3)
1. composition polymer barrier film with microcellular structure, it is characterized in that: added pore-foaming agent or/and inorganic powder, wherein pore-foaming agent is selected from low-molecular-weight polyethylene glycol, butanone, 1,4-butanediol, phosphoric acid, triethyl phosphate, ethylene glycol monoemethyl ether, poly-ethyl pyrrolidone, diethylamine, NaNO
3, LiCl, NH
4Cl; Inorganic powder is selected from AlN, Al
2O
3, BaTiO
3, LiNbO
3, LiAlO
2, Bi
2O
3, B
4C, BN, CaSiO
3, CeO
2, Fe
2O
3, MoS
2, PbTiO
3, SiC, Si
3N
4, SiO
2, TiB
2, TiO
2, WC, ZrO
2, MgO, AlBr
3, zeolite molecular sieve, glass fibre, the particle size of inorganic powder is 10nm-1 μ m; The basic structure of composition polymer barrier film is that pore-foaming agent or inorganic powder are distributed in polymer surfaces and inside or the barrier film hole, form the symmetry or the dissymmetrical structure of finger-like or spongy three-dimensional network, and aperture size, pattern with the difference of the kind of inorganic powder, particle diameter difference.
2. the described composition polymer barrier film of claim 1 is used as the barrier film of lithium secondary battery or ultrafiltration, the micro-filtration membrane that liquid liquid separates.
3. a method for preparing the described composition polymer barrier film of claim 1 is characterized in that, comprises following method:
(1) adopts control evaporation-immersion precipitation mixing method: polymer and inorganic powder, solvent and non-solvent are mixed, heating stirs into an even gel liquid, inorganic powder accounts for 0.2-6%, polymer accounts for 10-12%, solvent accounts for 75-84%, non-solvent accounts for 5-10%, and the method is used lower, the volatile solvent of boiling point; After static 2-20min sloughs bubble, under the room temperature condition coagulant liquid is coated on clean glass plate, polyester or the metal matrix by roll-in, blade coating, curtain coating or casting method; Coagulant liquid at humidity 30-80%, is solidified 0-20min under temperature 20-45 ℃ the condition, form nascent film; Then nascent symphysis is contained in the coagulating bath of 0-50% solvent with the matrix immersion, form wet film, coagulation bath temperature is lower than solvent boiling point, immerses time 10min-12hr; Take out wet film after air drying is removed most of water, put into vacuum drying oven 30-100 ℃ again and promptly obtain aperture size 5-20 μ m behind the dry 0.5-24hr down, porosity 40-80%, thickness are the composition polymer barrier film of 20-300 μ m; Or
(2) adopt immersion precipitation: polymer, inorganic powder, pore-foaming agent and solvent heating are stirred to are the transparent and homogeneous coagulant liquid, polymer accounts for 10-25%, inorganic powder accounts for the 2-40% of polymer weight, pore-foaming agent accounts for the 0-30% of polymer weight, and the method is used higher solvent or higher boiling point and the lower boiling mixed solvent of boiling point; The coagulant liquid coating process obtains nascent film with control evaporation-immersion precipitation mixing method; It is placed on air drying with matrix, humidity 30-80%, temperature 20-45 ℃, drying time, 0-20min contained nascent symphysis in the coagulating bath of 0-50% solvent with the matrix immersion then, and coagulation bath temperature is lower than solvent boiling point, immerses time 10min-12hr; Again film is put into 30-100 ℃ the dry 0.5-24hr of vacuum drying chamber subsequently, or in 55-65 ℃ the hot bath, removed residual solvent, rock-steady structure, the composition polymer membrane pore size size 20nm-20 μ m that the method makes, porosity is 3-70%; Or
(3) adopt the vapor phase precipitation method: polymer, inorganic powder, solvent heating are stirred to and are the transparent and homogeneous coagulant liquid, and polymer accounts for 10-30%, and inorganic powder accounts for the 2-40% of polymer weight; Being coated in the pre-saturated obturator of solvent vapour of coagulant liquid carried out, and temperature remains on 20 ℃ in the device, and feeds the nitrogen current that is mixed with the non-solvent steam; Regulate non-solvent steam and nitrogen relative scale, make the former scope be controlled at 65-100%; Coagulant liquid is coated on clean glass plate, polyester or the metal matrix by roll-in or blade coating; The symphysis that coats is placed 3-8hr with matrix in this device, and then immerse 20 ℃ non-solvent bathe in the 30min-4hr rock-steady structure, the method makes aperture size 5-20 μ m, porosity 20-70%, symmetrical decorticate composition polymer barrier film.
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|---|---|---|---|
| CNB031008135A CN1257564C (en) | 2003-01-22 | 2003-01-22 | Composite polymer diaphram used for secondary lithium battery and its preparation technology |
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|---|---|---|---|
| CNB031008135A CN1257564C (en) | 2003-01-22 | 2003-01-22 | Composite polymer diaphram used for secondary lithium battery and its preparation technology |
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|---|---|---|---|---|
| KR100647966B1 (en) * | 2004-02-24 | 2006-11-23 | 가부시키가이샤 도모에가와 세이시쇼 | Separator for electronic components and process for producing the same |
| CN100388532C (en) * | 2005-09-28 | 2008-05-14 | 浙江工业大学 | Diaphragn additive for lithium secondary cell and lithium secondary cell diaphragm |
| EP2328209B1 (en) * | 2008-09-12 | 2015-07-01 | Japan Vilene Company, Ltd. | Separator for lithium ion secondary battery, method for manufacture thereof, and lithium ion secondary battery |
| FR2958190B1 (en) * | 2010-04-01 | 2012-05-18 | Commissariat Energie Atomique | PROCESS FOR FORMING VINYLIDENE POLYFLUORIDE-TYPE FLUORINE POLYMER FILM USED AS LITHIUM BATTERY SEPARATOR |
| US9211506B2 (en) * | 2010-09-02 | 2015-12-15 | The University Of Hong Kong | Doping of inorganic minerals to hydrophobic membrane surface |
| CN103311486B (en) * | 2013-05-14 | 2016-06-08 | 中南大学 | A kind of organic-inorganic composite diaphragm and Synthesis and applications thereof |
| CN103468210A (en) * | 2013-09-25 | 2013-12-25 | 深圳市旭冉电子有限公司 | Abrasive and coating slurry of lithium-ion power battery diaphragm and preparation methods thereof |
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| CN103700796A (en) * | 2013-12-05 | 2014-04-02 | 宁波华丰包装有限公司 | Preparation method of lithium ion diaphragm |
| CN104979516B (en) * | 2014-04-10 | 2018-08-03 | 宁德时代新能源科技股份有限公司 | Electrochemical device and method for producing electrochemical device separation film |
| CN105449262A (en) * | 2014-06-30 | 2016-03-30 | 东莞新能源科技有限公司 | Flexible lithium ion battery and preparation method thereof |
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| CN106025149A (en) * | 2016-06-30 | 2016-10-12 | 深圳中兴创新材料技术有限公司 | High-temperature-resistant composite lithium battery diaphragm and preparation method for same |
| CN109065816A (en) * | 2018-08-14 | 2018-12-21 | 湘潭大学 | A kind of polyurethane-nano material composite diaphragm and Preparation method and use |
| CN109786624A (en) * | 2019-01-16 | 2019-05-21 | 北京卫蓝新能源科技有限公司 | A kind of preparation method and ion battery of ion battery porous septum |
| CN111916617A (en) * | 2019-05-10 | 2020-11-10 | 湖南农业大学 | Cellulose-based functionalized diaphragm and preparation method and application thereof |
| CN113839143A (en) * | 2021-08-02 | 2021-12-24 | 兰溪聪普新材料有限公司 | Polyarylethersulfone lithium ion battery diaphragm and preparation method thereof |
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